CN106414320A - Carbon nanotube dispersion liquid, conductor film and conductive film - Google Patents
Carbon nanotube dispersion liquid, conductor film and conductive film Download PDFInfo
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- CN106414320A CN106414320A CN201580005482.2A CN201580005482A CN106414320A CN 106414320 A CN106414320 A CN 106414320A CN 201580005482 A CN201580005482 A CN 201580005482A CN 106414320 A CN106414320 A CN 106414320A
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Abstract
The purpose of the present invention is to provide a carbon nanotube dispersion liquid which has excellent stability and is capable of forming a conductor film that exhibits excellent adhesion to a base. A carbon nanotube dispersion liquid according to the present invention is characterized by containing (A) carbon nanotubes, (B) a polymer dispersant that contains a sulfonic acid group-containing monomer unit and an ethylenically unsaturated aliphatic carboxylic acid monomer unit, and (C) a solvent. This carbon nanotube dispersion liquid is also characterized in that the content ratio of the ethylenically unsaturated aliphatic carboxylic acid monomer unit in the polymer dispersant (B) is more than 20% by mole but 90% by mole or less.
Description
Technical field
The present invention relates to carbon nano tube dispersion liquid, conducting film and conductive film.
Background technology
CNT (hereinafter also referred to " CNT ") is each due to electric conductivity, electrical conductivity, mechanical strength etc.
Plant excellent, inquire into various industrial applications in the past.For example, it is conceived to its excellent conduction
Property, inquired into the technology forming conducting film using CNT in the past.
The conducting film comprising CNT can be formed on base material by following manner：For example, on base material
Coating by CNT, solvent and makes the carbon that CNT is dispersed in the cooperation of the dispersant in solvent receive
Mitron dispersion liquid (hereinafter also referred to " CNT dispersion "), and the CNT dispersion on base material is dried.
And then, for the conductive film improving such conducting film and conducting film is possessed on base material
Performance, has attempted dispersant and CNT dispersion used in the formation to conducting film and has been improved.
For example, report in patent documentation 1 and possess following layers, there is specific light transmittance and surface electricity
The transparent and electrically conductive film of resistance rate, its durability is high, have high conductivity and light transmission is excellent, described layer bag
Containing by CNT and on the conducting film that formed as the aromatic polymer of dispersant and this conducting film
Resin bed.
In addition, for example reporting the description below in patent documentation 2：With respect to CNT with special ratios
The number-average molecular weight comprising polysaccharide etc. is more than 10,000 and less than 150,000 dispersant and adjusts pH
The CNT dispersion of the aqueouss to particular range, while keeping polymolecularity, cuts with respect to height
The excellent in stability of shear force.
Additionally, for example reporting the description below in patent documentation 3：Comprise respectively with ad hoc structure formula table
The Malaysia of substituted or unsubstituted aromatic hydrocarbyl is had on the styrene sulfonic acid monomer residue that shows, nitrogen-atoms
Acid imide residue and from itaconic acid and fumaric acid etc. other vinyl monomer residues as repetitive structure
Unit, and the content ratio of each residue is respectively 30～95 moles of %, 5～70 moles of %, 0～20 rubs
The polystyrene sulfonate copolymer of your %, makes the scattered ability such as CNT stronger in an aqueous medium.
Prior art literature
Patent documentation
Patent documentation 1：Japanese Unexamined Patent Publication 2009-163959 publication
Patent documentation 2：Japanese Unexamined Patent Publication 2013-199419 publication
Patent documentation 3：International Publication No. 2013/042482
Content of the invention
Problems to be solved by the invention
Here, the electric conductivity of the conductive film in order to ensure obtaining, mechanical property and transparency etc. it is desirable to
Used in the formation of conducting film, CNT dispersion has the excellent stable of the cohesion that can suppress CNT etc.
Property.Additionally, for the conducting film being formed by CNT dispersion, also requiring, with base material, there is excellent gluing
Connecing property.
But, in above-mentioned prior art, the stability of CNT dispersion and being disperseed by CNT
The conducting film that liquid is formed is insufficient with the cementability of base material.Therefore, above-mentioned prior art is improving CNT
The stability of dispersion liquid and the cementability aspect with base material of the conducting film being formed by CNT dispersion, still
There is room for improvement.
Therefore, it is an object of the invention to provide excellent in stability and can be formed bonding with base material
The carbon nano tube dispersion liquid of the excellent conducting film of property.
In addition, it is an object of the invention to provide with conducting film base material excellent in adhesion and possessing
The conductive film of this conducting film.
The method of solve problem
The present inventor has made intensive studies to achieve these goals.And then, the present inventor etc. finds：
When making CNT be scattered in solvent, by using the macromolecule dispersing agent conduct being formed by following polymer
Dispersant, can be in suppressing CNT dispersion while the cohesion of CNT, using this dispersion liquid shape
Conducting film and the base material becoming excellent in adhesion, described polymer contain monomeric unit containing sulfonic group and
Contain olefinic unsaturated aliphatic carboxylic monomer unit with special ratios.And then complete the present invention.
That is, it is an object of the invention to the above-mentioned problem of effectively solving, the carbon nano tube dispersion liquid bag of the present invention
Carbon nanotubes (A), contain monomeric unit containing sulfonic group and olefinic unsaturated aliphatic carboxylic monomer unit
Macromolecule dispersing agent (B) and solvent (C), wherein, in above-mentioned macromolecule dispersing agent (B), above-mentioned olefinic is not
The content ratio of representative examples of saturated aliphatic carboxylic monomeric unit is higher than 20 moles of % and is 90 moles of below %.As
Fruit like this, as being used for making the scattered dispersant of CNT, using containing monomeric unit containing sulfonic group,
And contain the macromolecule dispersing agent of olefinic unsaturated aliphatic carboxylic monomer unit with special ratios, then may be used
Excellent in stability and being formed is provided to divide with the CNT of conducting film base material excellent in adhesion
Dispersion liquid.
It should be noted that in the present invention, described " containing ... monomeric unit " refers to, " makes
The construction unit from this monomer is contained " in the polymer being obtained with monomer.
Here, for the carbon nano tube dispersion liquid of the present invention, upper in above-mentioned macromolecule dispersing agent (B)
State the monomeric unit that monomeric unit containing sulfonic group is preferably derived from aromatic sulphonic acid or its salt.If macromolecule
Dispersant (B) contain from aromatic sulphonic acid or its salt monomeric unit as monomeric unit containing sulfonic group,
The stability of CNT dispersion then can be made more excellent.
And then, for the carbon nano tube dispersion liquid of the present invention, upper in above-mentioned macromolecule dispersing agent (B)
State olefinic unsaturated aliphatic carboxylic monomer unit to be preferably derived from selected from acrylic acid, methacrylic acid, horse
Carry out the monomeric unit of at least one in sour, fumaric acid, itaconic acid and their salt.If fractionated polymer
Powder (B) is containing the monomeric unit from above-mentioned any monomer as olefinic unsaturated aliphatic carboxylic acid monomer
Unit, then can make the stability of CNT dispersion more excellent.
In addition, for the carbon nano tube dispersion liquid of the present invention, in preferably above-mentioned macromolecule dispersing agent (B)
The above-mentioned content ratio containing sulfonic group monomeric unit be 10 moles of % less than 80 moles of %.As
Fruit macromolecule dispersing agent (B) contains monomeric unit containing sulfonic group with aforementioned proportion, then CNT can be made to disperse
The cementability with base material of the stability of liquid and the conducting film being formed by this dispersion liquid is more excellent.
Further, for the carbon nano tube dispersion liquid of the present invention, preferably above-mentioned macromolecule dispersing agent (B)
In the above-mentioned content ratio containing sulfonic group monomeric unit single with above-mentioned olefinic unsaturated aliphatic carboxylic acid monomer
The ratio of the content ratio of unit is 0.5 less than 4.If list containing sulfonic group in macromolecule dispersing agent (B)
The ratio of the content ratio of body unit and the content ratio of olefinic unsaturated aliphatic carboxylic monomer unit is upper
In the range of stating, then can make the stability of CNT dispersion and the conducting film being formed by this dispersion liquid
The cementability with base material more excellent.
And then, for the carbon nano tube dispersion liquid of the present invention, preferably above-mentioned CNT (A) comprises list
At least one of wall carbon nano tube and double-walled carbon nano-tube.If using SWCN and double-walled carbon
At least one of nanotube (being also referred to as " single wall CNT ", " double-walled CNT " below) conduct
CNT, then can make the electric conductivity of conducting film that formed by CNT dispersion and mechanical property excellent.
In addition, for the carbon nano tube dispersion liquid of the present invention, preferably above-mentioned solvent (C) comprise water and
And the pH of this carbon nano tube dispersion liquid is more than 0.1 and less than 8.If use water as solvent and
And the pH of this carbon nano tube dispersion liquid is more than 0.1 and less than 8, then can make the steady of CNT dispersion
Qualitative more excellent.
Here, for the carbon nano tube dispersion liquid of the present invention, preferably with respect to CNT (A) every 100
Mass parts, comprise the above-mentioned macromolecule dispersing agent (B) of below more than 50 mass parts and 1000 mass parts.
If the use level with respect to CNT for the macromolecule dispersing agent (B) is within the above range, CNT can be made
The cementability with base material of the stability of dispersion liquid and the conducting film being formed by CNT dispersion is more
Excellent.
In addition, it is an object of the invention to the above-mentioned problem of effectively solving, the conducting film of the present invention is using upper
State obtained from any one carbon nano tube dispersion liquid.If using the CNT dispersion of the present invention, can
To provide and conducting film base material excellent in adhesion.
Here, it is preferred that the surface resistivity of the conducting film of the present invention is 20 Ω/below.If conducting film
Surface resistivity within the above range, then can make the conductive film for example possessing this conducting film on base material
Excellent electric conductivity.
In addition, it is an object of the invention to the above-mentioned problem of effectively solving, the conductive film of the present invention possesses base
Conducting film on material and described base material, wherein, described conducting film is any of the above-described kind of conducting film.Possesses this
The conductive film of the conducting film of invention has excellent electric conductivity.
The effect of invention
According to the present invention it is possible to providing excellent in stability and being formed excellent in adhesion with base material
Conducting film carbon nano tube dispersion liquid.
In addition, according to the present invention it is possible to providing and conducting film base material excellent in adhesion and possessing
The conductive film of this conducting film.
Specific embodiment
Hereinafter, embodiments of the present invention are described in detail.
Here, the carbon nano tube dispersion liquid of the present invention is used for the formation of conducting film.In addition, the present invention's leads
Electrolemma is formed by the carbon nano tube dispersion liquid of the present invention.And then, the conductive film of the present invention is on base material
Possesses the conducting film of the present invention.
(carbon nano tube dispersion liquid)
The carbon nano tube dispersion liquid of the present invention comprises：CNT (A), macromolecule dispersing agent (B) and molten
Agent (C).Wherein, this macromolecule dispersing agent (B) is characterised by：Contain monomeric unit containing sulfonic group, and
And olefinic unsaturated aliphatic carboxylic monomer unit is contained with specific content ratio.The carbon nanometer of the present invention
The excellent in stability of pipe dispersion liquid, in addition, the conducting film being formed by this carbon nano tube dispersion liquid and base material
Excellent in adhesion.Hereinafter, each composition comprising in the CNT dispersion of the present invention is described in detail.
It should be noted that in this manual, also by " CNT (A) " be referred to as " CNT (A) ",
Also by the " fractionated polymer containing monomeric unit containing sulfonic group and olefinic unsaturated aliphatic carboxylic monomer unit
Powder (B) " is referred to as " macromolecule dispersing agent (B) ".
<CNT (A)>
CNT (A) can also be able to be both multi-walled carbon nano-tubes for SWCN, but from improve by
From the viewpoint of the electric conductivity of conducting film of CNT dispersion formation, mechanical property, preferably comprise single wall
At least one of CNT and double-walled carbon nano-tube, more preferably comprise SWCN.
In addition, for CNT (A), when being evaluated using Raman spectroscopy, preferably it has Radial
The peak of Breathing Mode (radial breathing modes, RBM).It should be noted that more than three walls
In the Raman spectrum of multi-walled carbon nano-tubes, there is not RBM.
Further, G in Raman spectrum for the CNT (A) carries peak strength and D to carry the ratio of peak strength
(G/D ratio) is preferably more than 1 and less than 20.If G/D is than for more than 1 and less than 20, even if
The use level of CNT (A) is a small amount of it is also possible to fully improve leading of the conducting film being formed by CNT dispersion
Electrically, mechanical property.
In addition, the diameter Distribution (3 σ) of CNT (A) is preferably greater than 0.20 with the ratio (3 σ/Av) of average diameter (Av)
And it is less than 0.60, more preferably greater than 0.25, further preferably greater than 0.50.If be more than using 3 σ/Av
0.20 and less than 0.60 CNT, even if then the use level of CNT (A) is a small amount of, also can fully improve by
The electric conductivity of conducting film of CNT dispersion formation, mechanical property.
It should be noted that described " diameter Distribution (3 σ) " refers to, the sample mark of the diameter of CNT
Quasi- deviation (σ) is multiplied by value obtained from 3.Wherein, " average diameter (Av) of CNT " and " carbon is received
The sample standard deviation (σ) of the diameter of mitron " can be randomly choosed using determination of transmission electron microscopy respectively
The diameter of 100 CNTs and obtain.
Here, the average diameter (Av) of CNT (A) be preferably more than 0.5nm, further preferred 1nm with
On, preferably below 15nm, further preferred below 10nm.If the average diameter (Av) of CNT (A)
For more than 0.5nm, then can suppress the cohesion of CNT (A), improve stablizing of CNT dispersion further
Property.In addition, if the average diameter (Av) of CNT (A) be below 15nm, then can fully improve by
The mechanical property of the conducting film that CNT dispersion is formed.
It should be noted that the average diameter (Av) for above-mentioned CNT (A) and diameter Distribution (3 σ), permissible
By change the manufacture method of CNT, manufacturing condition and be adjusted it is also possible to by will be using difference
The CNT that manufacture method obtains carries out multiple combination to adjust.
Additionally, for CNT (A), following CNT is usually used：Using transmission electron microscope pair
The diameter of 100 CNT randomly choosing is measured, and takes a diameter of transverse axis, frequency to map for the longitudinal axis,
And during with Gaussian approximation, obtain the CNT of normal distribution.
In addition, specific surface area before adding to solvent (C) for the CNT (A) is preferably 600m2/ more than g,
This CNT (A) can be not opening, can also be opening.During for not opening CNT, specific surface
Long-pending preferably 800m2/ more than g, and preferably 1,200m2/ below g, more preferably 1,000m2/g
Below.On the other hand, be opening CNT when, specific surface area is preferably 1,300m2/ more than g, and excellent
Elect 2,500m as2/ below g, further preferred 2,300m2/ below g.If the specific surface area of CNT (A)
In 600m2/ more than g, then can improve well the conducting film being formed by CNT dispersion electric conductivity,
Mechanical property.Further, if the specific surface area of CNT (A) within the above range, can improve CNT
The stability of dispersion liquid.
It should be noted that in the present invention, specific surface area refers to the BET ratio based on nitrogen adsorption
Surface area.
Further, the weight density of CNT (A) is preferably 0.002g/cm3Above and 0.2g/cm3Below.
If weight density is 0.2g/cm3Hereinafter, then CNT (A) combination to each other dies down, and therefore can make
CNT (A) is more uniformly dispersing.In addition, if weight density is 0.002g/cm3More than, then due to
The integraty that CNT (A) can be made improves, suppresses at random, and therefore operation becomes easy.
Additionally, it is preferred that CNT (A) has multiple micro hole.Wherein, to have aperture little for preferably CNT (A)
In the micropore of 2nm, as the amount of micropore, in terms of micropore volume, it is preferably more than 0.40mL/g,
More preferably more than 0.43mL/g, more preferably more than 0.45mL/g, as the upper limit, generally
For 0.65mL/g about.By making CNT (A), there is micropore as above, CNT (A) can be suppressed
Cohesion, improve containing CNT film in CNT (A) dispersibility, effectively obtain electric conductivity and machinery
The conducting film of excellent.It should be noted that micropore volume can be by for example suitably changing CNT (A)
Preparation method and preparation condition and be adjusted.
Here, described " micropore volume (Vp) " can be by measuring CNT under liquid nitrogen temperature (77K)
Nitrogen adsorption isotherm, the N2 adsorption amount under relative pressure P/P0=0.19 is set to V, and according to formula (I):
Vp=(V/22414) × (M/ ρ) and calculate.It should be noted that P is mensure pressure during adsorption equilibrium,
P0 is the saturated vapour pressure of liquid nitrogen when measuring, and in formula (I), M is the molecular weight of adsorbate (nitrogen)
28.010, ρ is density 0.808g/cm under the 77K of adsorbate (nitrogen)3.Micropore volume can use example
As " BELSORP (registered trade mark)-mini " [BEL Japan system] is easily obtained.
It should be noted that the CNT (A) with above-mentioned character can be manufactured effectively by following manner：
For example, by having the base material (hereinafter also referred to " CNT of CNT catalyst for producing oxidant layer to surface
Manufacture base material ") go up base feed compound and carrier gas and utilize chemical vapour deposition technique (CVD)
Make in system, there is micro oxidant (activation of catalyst material) during synthesis CNT, so that CNT system
Make with method (the Super-growth method (excusing from death regular way) that improves of the tremendous ground of the catalysis activity of catalyst layer；
With reference to International Publication No. 2006/011655) in, the shape in substrate surface for the catalyst layer is carried out by wet method
Become, and (for example, comprise the above acetylene of 50 volumes % using the unstrpped gas with acetylene as main component
Gas).Hereinafter, also the CNT obtaining by Super-growth method is referred to as " SGCNT ".
By using SGCNT as CNT (A), conducting film can be made more excellent with the cementability of base material.
For the concentration of the CNT (A) in the CNT dispersion of the present invention, as long as dispersion liquid can be formed then
It is not particularly limited, the concentration of the CNT in dispersion liquid is preferably more than 0.005 mass %, is more preferably
More than 0.01 mass %, more than more preferably 0.05 mass %, particularly preferably 0.1 mass % with
On, below preferably 20 mass %, below more preferably 10 mass %, even more preferably for 5 matter
Amount below %.
The excellent tribute as dispersant Ji Yu aftermentioned macromolecule dispersing agent (B) for the CNT dispersion of the present invention
Offer and have and have the advantage that：Compared with conventional CNT dispersion, even if CNT is coordinated with high concentration,
Also ensure that its stability.And then, by making CNT dispersion, CNT is comprised with high concentration, and make
Compared with the situation of conventional CNT dispersion, every list of base material can be made with less application frequency
The CNT coating weight that plane amasss rises to desired value.
<Macromolecule dispersing agent (B)>
In the CNT dispersion of the present invention, as dispersant, using containing monomeric unit containing sulfonic group,
And the macromolecule dispersion of olefinic unsaturated aliphatic carboxylic monomer unit is contained with specific content ratio
Agent.
By using such macromolecule dispersing agent, coagulating of CNT in CNT dispersion (A) can be suppressed
Gather, make the excellent in stability of CNT dispersion.In addition, just by the CNT comprising this macromolecule dispersing agent (B)
For the conducting film that dispersion liquid is formed, based on contained sulfonic group in this macromolecule dispersing agent and carboxyl this two
The contribution of person and there is the superior adhesion with base material.
Additionally, in general, dispersant mostly can become impedance after conducting film formation and lead to conduction
The electric conductivity of film reduces.But because used in the present invention, macromolecule dispersing agent (B) can extremely well make
CNT (A) disperses, and the therefore CNT dispersion according to the present invention can not be subject to as impedance factors
The impact of dispersant, there is the conducting film of superior electrical conductivity.
Hereinafter, the monomer that can form the monomeric unit constituting macromolecule dispersing agent (B) is described in detail.
[monomer containing sulfonic group]
As the monomer containing sulfonic group containing sulfonic group monomeric unit that can form macromolecule dispersing agent (B), only
Sulfonic group to be had and carbon-to-carbon unsaturated bond etc. can with the monomer of the group of other monomer copolymerizations,
It is not particularly limited, can enumerate for example：The aromatic sulphonic acids such as styrene sulfonic acid, vinyl sulfonic acid, allyl
Base sulfonic acid, acrylamide-tert-butyl group sulfonic acid, acryloyl amine-n-butane sulfonic acid etc..It should be noted that
Here, for monomer containing sulfonic group, the hydrogen atom in its sulfonic group can also be by inorganic ionss or organic
Ionic replacement and become the form of inorganic salt or organic salt.That is, monomer containing sulfonic group can be sulfonate
Form.
As inorganic salt, alkali metal salt (lithium, sodium, potassium etc.) etc. can be enumerated, as organic salt, can enumerate：
Alkylamine salt (methylamine, ethamine, propylamine, butylamine, dimethylamine, diethylamine, trimethylamine, tripropyl amine (TPA),
Tri-n-butylamine, tri-tert amine etc.), aryl amine salt (phenyl amine, benzyl amine etc.) etc..These lists containing sulfonic group
Body can be used alone one kind it is also possible to be applied in combination more than two kinds.
And then, in these, from the viewpoint of the stability improving CNT dispersion, as containing sulfonic acid
Base monomer, the aromatic sulphonic acid such as optimization styrene sulfonic acid, vinyl sulfonic acid, acrylamide-tert-butyl group sulphur
Acid and their alkali metal salt (sodium, potassium), more preferably styrene sulfonic acid, vinyl sulfonic acid and they
Alkali metal salt (sodium, potassium).
It should be noted that containing the content ratio of sulfonic group monomeric unit in macromolecule dispersing agent (B) (containing sulphur
Acid-based monomers unit accounts for the ratio of whole monomeric units) be usually 10 moles of % rub less than 80
You are %, preferably 20 moles more than %, more preferably 30 moles more than %, particularly preferably 40 moles of %
More than, preferably 70 moles below %, more preferably 60 moles of below %.If macromolecule dispersing agent
(B) contain the content ratio of sulfonic group monomeric unit within the above range, then can make CNT dispersion
Stability and the conducting film that formed by this dispersion liquid excellent in adhesion with base material.
[olefinic unsaturated aliphatic carboxylic acid monomer]
Olefinic as the olefinic unsaturated aliphatic carboxylic monomer unit that can form macromolecule dispersing agent (B)
Unsaturated aliphatic carboxylic acid monomer, as long as can be with the fat with carbon-to-carbon double bond of other monomer copolymerizations
Aliphatic carboxylic acid, is not particularly limited, and can enumerate：Acrylic acid, methacrylic acid, maleic acid, richness
Horse acid, itaconic acid etc..It should be noted that here, for olefinic unsaturated aliphatic carboxylic acid monomer,
Hydrogen atom in its carboxyl can also be replaced and become inorganic salt or organic by inorganic ionss or organic ion
The form of salt.That is, olefinic unsaturated aliphatic carboxylic acid monomer can be the form of carboxylate.Here, make
For inorganic salt, organic salt, can enumerate with the identical enumerated in the item of above-mentioned [monomer containing sulfonic group] that
A bit.These olefinics unsaturated aliphatic carboxylic acid monomer may be used alone, can also be used in combination two kinds with
On.
If it should be noted that macromolecule dispersing agent (B) has from olefinic unsaturated aliphatic carboxylic acid
The repetitive structure of monomer, then with have from olefinic unsaturation aromatic carboxylic acid monomer (N- carboxyl phenyl horse
Come acid imide, 4- vinyl benzoic acid etc.) the situation of structure compare, can make big with the cementability of base material
Width improves.
And then, as olefinic unsaturated aliphatic carboxylic acid monomer, from the stability improving CNT dispersion
From the viewpoint of, preferably acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and they
Salt, more preferably acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and their alkali gold
Belong to salt (sodium, potassium).
It should be noted that in macromolecule dispersing agent (B), olefinic unsaturated aliphatic carboxylic monomer unit
Content ratio (olefinic unsaturated aliphatic carboxylic monomer unit accounts for the ratio of whole monomeric units) need height
In 20 moles of % and be 90 moles of below %, preferably 25 moles more than %, more preferably 30 moles %
More than, particularly preferably 40 moles more than %, and preferably 80 moles below %, more preferably 70
Mole below %, particularly preferably 60 moles below %.If olefinic insatiable hunger in macromolecule dispersing agent (B)
Content ratio with aliphatic carboxylic acid monomeric unit is 20 moles of below %, then cannot guarantee and base material
Cementability, if above 90 moles of %, then cannot guarantee dissolubility in a solvent and the dispersion of CNT
The having both of property.
[monomer containing sulfonic group/olefinic unsaturated aliphatic carboxylic acid monomer's mol ratio]
Here, in macromolecule dispersing agent (B), the content ratio (mole %) containing sulfonic group monomeric unit is relatively
In olefinic unsaturated aliphatic carboxylic monomer unit content ratio (mole %) ratio (also referred to as " containing sulfonic acid
Base monomer/olefinic unsaturated aliphatic carboxylic acid monomer's mol ratio ") it is preferably more than 0.5, more preferably 1
More than, preferably shorter than 4, more preferably less than 3.By making monomer containing sulfonic group/olefinic unsaturated fatty acidss
Race's carboxylic acid monomer's mol ratio within the above range, can make the stability of CNT dispersion and by CNT
Dispersion liquid formed conducting film excellent in adhesion with base material.
[other monomer]
As long as significantly not destroying the effect of the present invention, except above-mentioned containing sulfonic group in macromolecule dispersing agent (B)
Beyond monomeric unit, olefinic unsaturated aliphatic carboxylic monomer unit, can also comprise arbitrarily to repeat list
Unit.As the other monomers that can form such arbitrary repetitives, can enumerate：Acrylate (third
E pioic acid methyl ester, ethyl acrylate, propyl acrylate, butyl acrylate, benzyl acrylate etc.), methyl
Acrylate (methyl methacrylate, ethyl methacrylate, propyl methacrylate, metering system
Acid butyl ester, benzyl methacrylate etc.), itaconate (itaconic acid methyl ester, itaconic acid ethyl ester, itaconic acid
Propyl ester, itaconic acid n-butyl, itaconic acid benzyl ester etc.), styrene, acrylonitrile, methacrylonitrile, propylene
Amide, Methacrylamide, clothing health amide, N, N- DMAA etc..
It should be noted that in macromolecule dispersing agent (B), except monomeric unit containing sulfonic group, olefinic insatiable hunger
It is preferably 30 moles of below % with the content ratio of the monomeric unit beyond aliphatic carboxylic acid monomeric unit,
More preferably 20 moles of below %, more preferably 10 moles %, particularly preferably 5 moles % with
Under.
[preparation of macromolecule dispersing agent (B)]
Additionally, macromolecule dispersing agent (B) can be by for example making the monomer composition comprising above-mentioned monomer anti-
Answer and be polymerized in solvent and manufacture.
Here, the content ratio (accounting for the ratio (mole %) of whole monomers) of each monomer in monomer composition
Content ratio generally with corresponding monomeric unit (repetitives) in desired (B) in macromolecule dispersing agent
(accounting for the ratio (mole %) of whole monomeric units) is identical.
For reaction dissolvent, polymerization, polymerization initiator etc., can suitably select known those
And it is used for the preparation of macromolecule dispersing agent (B).
It should be noted that each monomeric unit in macromolecule dispersing agent (B) accounts for the ratio of whole monomeric units
Example (mole %) can utilize1H-NMR analysis is measured.
[character of macromolecule dispersing agent]
The number-average molecular weight of macromolecule dispersing agent (B) is not particularly limited, but preferably more than 1,000,000,
More preferably more than 2,000,000, more preferably more than 3,000,000, and preferably less than 25,000,000,
More preferably less than 15,000,000, more preferably less than 10,000,000.Here, macromolecule dispersing agent
Number-average molecular weight can be gathered with based on standard by using the gel permeation chromatography using water as eluent
The calibration trace of ethylene glycol carries out comparison to calculate.
Hereinafter describe the concrete example of macromolecule dispersing agent (B), but the macromolecule dispersing agent that the present invention uses
(B) it is not limited to this.(it should be noted that in bracket after each monomer name in following illustration
The numerical value recorded, represents the content ratio of the monomeric unit being derived from this monomer in each macromolecule dispersing agent (B)
(mole %), described " mol ratio " represents the mol ratio of each monomeric unit in each macromolecule dispersing agent (B))
D-1) copolymer (mol ratio=1/1, the average degree of polymerization of Sodium styrene sulfonate (50)/sodium acrylate (50)
20000, number-average molecular weight 3,000,000 2300)
D-2) Sodium styrene sulfonate (50)/Sodium methacrylate. (50) copolymer (mol ratio=1/1, averagely poly-
Right 30,000, number-average molecular weight 4,720,000 8500)
D-3) copolymer of Sodium styrene sulfonate (66.7)/methacrylic acid potassium (33.3) (put down by mol ratio=2/1
All degree of polymerization 50,000, number-average molecular weight 8,710,000 0400)
D-4) copolymer (mol ratio=3/1, the average polymerization of Sodium styrene sulfonate (75)/itaconic acid disodium (25)
Spend 50,000, number-average molecular weight 9,900,000 7800)
D-5a) Sodium styrene sulfonate (50)/Malaysia acid disodium (50) copolymer (mol ratio=1/1, averagely poly-
Right 20,000, number-average molecular weight 3,660,000 2300)
D-5b) Sodium styrene sulfonate (50)/Malaysia acid disodium (50) copolymer (mol ratio=1/1, averagely poly-
Right 50,000, number-average molecular weight 9,150,000 5700)
D-5c) Sodium styrene sulfonate (50)/Malaysia acid disodium (50) copolymer (mol ratio=1/1, averagely poly-
Right 90,000, number-average molecular weight 16,480,000 0300)
D-6) copolymer (mol ratio=3/1, the average polymerization of Sodium styrene sulfonate (75)/Malaysia acid disodium (25)
Spend 20,000, number-average molecular weight 3,890,000 3000)
D-7) copolymer (mol ratio=1/1, the average polymerization of styrene sulfonic acid ammonium (50)/maleic acid diammonium (50)
Spend 30,000, number-average molecular weight 5,260,000 6700)
D-8) copolymer (mol ratio=1/1, the average degree of polymerization 2 of styrene sulfonic acid (50)/maleic acid (50)
Ten thousand, number-average molecular weight 3,220,000 2000)
D-9) copolymer (mol ratio=1/1, the average polymerization of Sodium styrene sulfonate (50)/Disodium fumarate. (50)
Spend 20,000, number-average molecular weight 3,660,000 3300)
D-10) copolymer (mol ratio=1/1, the average polymerization of sodium vinyl sulfonate (50)/sodium acrylate (50)
Spend 50,000, number-average molecular weight 2,240,000 1400)
D-11) copolymer (mol ratio=1/1, the average polymerization of sodium allylsulfonate (50)/sodium acrylate (50)
Spend 20,000, number-average molecular weight 2,380,000 1600)
D-12) acryloyl amine-n-sodium butane sulfonate (50)/sodium acrylate (50) copolymer (mol ratio=1/1,
Average degree of polymerization 80,000, number-average molecular weight 12,050,000 1600)
D-13) Sodium styrene sulfonate (40)/Malaysia acid disodium (40)/acrylamide (20) copolymer (mole
Ratio=2/2/1, average degree of polymerization 30,000, number-average molecular weight 5,570,000 7300)
D-14) the copolymer of Sodium styrene sulfonate (40)/Malaysia acid disodium (40)/maleic acid monomethyl sodium (20)
(mol ratio=2/2/1, average degree of polymerization 1.5 ten thousand, number-average molecular weight 2,970,000 7600)
D-15) copolymer of Sodium styrene sulfonate (50)/Malaysia acid disodium (33.3)/sodium acrylate (16.7) (rubs
That ratio=3/2/1, average degree of polymerization 2.5 ten thousand, number-average molecular weight 4,970,000 7300)
The concentration of the macromolecule dispersing agent (B) in the CNT dispersion of the present invention is preferably 0.0001 mass %
More than, more than more preferably 0.01 mass %, more than particularly preferably 0.05 mass %, preferably 30
Below quality %, below more preferably 10 mass %, below particularly preferably 5 mass %.By making height
The concentration of dispersal agent molecule (B) is more than 0.0001 mass %, can improve the stability of CNT dispersion
And the cementability with base material of the conducting film being formed by this CNT dispersion, by for 30 mass % with
Lower it can be ensured that the electric conductivity of the conducting film being formed by CNT dispersion.
And then, with respect to every 100 mass parts of CNT (A), high score in the CNT dispersion of the present invention
The content of sub- dispersant (B) is preferably more than 50 mass parts, more than more preferably 100 mass parts, preferably
Below 1000 mass parts, below more preferably 700 mass parts, particularly preferably 400 mass parts with
Under.By making to comprise 50 mass parts with respect to every 100 mass parts of CNT (A) in CNT dispersion
Above macromolecule dispersing agent (B), can improve the stability of CNT dispersion and be divided by this CNT
The cementability with base material of the conducting film that dispersion liquid is formed, by comprising the macromolecule of below 1000 mass parts
Dispersant (B) is it can be ensured that the electric conductivity of the conducting film being formed by CNT dispersion.
Even if it should be noted that being applied in combination above-mentioned macromolecule dispersion in the CNT dispersion of the present invention
Other dispersants beyond agent (B) also have no problem, and in order to improve dispersibility, use for a combination thereof
Do not limit.As other dispersants, can use：Various ionic, nonionic surfactants,
Synthesis macromolecule beyond above-mentioned macromolecule dispersing agent (B), natural polymer etc..
<Solvent (C)>
Solvent (C) can also can be organic solvent class for aqueouss, but it is (that is, excellent to preferably use aqueous solvent
Solvent (C) is selected to comprise water).Here.As aqueous solvent, as long as wherein dispersibling the solvent of CNT then
Have no particular limits, can be used alone water, it is possible to use the mixing of the solvent mixing with water is molten
Agent.As the solvent mixing with water, can enumerate：Ethers (dioxane, oxolane, methyl cellosolve
Deng), ether alcohol (ethoxy ethanol, methoxyethoxy ethanol etc.), esters (methyl acetate, ethyl acetate
Deng), ketone (Ketohexamethylene, butanone etc.), alcohols (ethanol, isopropanol, phenol etc.), low-grade carboxylic acid's (second
Acid etc.), amine (triethylamine, trimethanolamine etc.), nitrogenous polar solvent (N,N-dimethylformamide, nitre
Methylmethane, N-Methyl pyrrolidone, acetonitrile etc.), sulphur compound class (dimethyl sulfoxide etc.) etc..In these,
As the solvent mixing with water, from the viewpoint of the stability improving CNT dispersion, preferably ethers,
Alcohols, N,N-dimethylformamide.
In the case that the solvent (C) of CNT dispersion comprises water, there is no spy to the pH of CNT dispersion
Do not limit, preferably more than 0.1, more preferably more than 0.2, particularly preferably more than 0.5, preferably
For less than 8, more preferably less than 7 (i.e. acid), more preferably less than 5, particularly preferably 2.5
Below.By make the pH of CNT dispersion within the above range it can be ensured that CNT dispersion steady
Qualitative.
It should be noted that for the pH reducing CNT dispersion, adding acidic materials.As
Acidic materials, preferably use for example sulphuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid, tartaric acid, formic acid,
Phosphoric acid etc., more preferably hydrochloric acid, nitric acid.
<The preparation of carbon nano tube dispersion liquid>
The CNT dispersion of the present invention can be by for example using Japanese Unexamined Patent Publication 2013-199419 publication
Described in mixing dispersion machine make CNT (A), macromolecule dispersing agent (B) and solvent (C) mixing and prepare.
Wherein, easier using ultrasonic homogenizer, therefore preferably.During mixing, CNT (A) can be for being dried shape
State or the solvent-laden state of bag.In addition, CNT dispersion is liquid or paste, gel
Such semisolid shape, but preferably liquid.
(conducting film and conductive film)
The conducting film of the present invention is to be formed using the CNT dispersion of the present invention.Such conducting film
Excellent in adhesion with base material.The conducting film of the present invention is excellent due to operability, is therefore suitable in base
The purposes of the conductive film of this conducting film is formed on material.
<Base material>
For base material, as long as can thereon carbon nanotubes dispersion liquid, gained can be loaded lead
Electrolemma, is not particularly limited to its shape, constituent material and size (thickness etc.), can be according to mesh
Target purposes is suitably selected.
As the shape of base material, can enumerate for example：Film, piece etc..
Constitute among the material of base material, as inorganic material, can enumerate：Rustless steel, aluminum, ferrum, gold,
The metals such as silver and glass etc..As organic material, material with carbon element, plastic substrate material etc. can be enumerated, but
Go out from the stretching tracing ability of the cementability improving with conducting film and conductive film and the viewpoint of flexibility
Send out, preferably plastic substrate material.Further, as plastic substrate material, preferably thermostability is high, resistance to
Medicine and gas blocking is excellent and the material of low cost.In addition, plastic substrate material can be no
Colour and there is transparent material.As such specific plastic substrate material, it is possible to use for example：
Polyesters (polyethylene terephthalate (PET), PEN (PEN) etc.), benzene second
Alkenes (syndiotactic polystyrene (SPS) etc.), polyphenylene sulfide (PPS), Merlon (PC), polyarylate
(PAr), polysulfones (PSF), polyester sulfone (PES), Polyetherimide (PEI), clear polyimides (PI), ring
Olefin copolymer (trade name " ARTON " (registered trade mark) etc.) and ester ring type polyolefin (trade name
" ZEONOR " (registered trade mark) etc.), Merlon, polyamide, polyurethane, poly-methyl methacrylate
Ester, cellulose, cellulose triacetate etc..Wherein, chemically from the viewpoint of stability and cost, special
Not preferably polyethylene terephthalate (PET), PEN (PEN), ester ring type do not gather
Alkene.
In the case that base material uses plastic substrate material, preferred base material thickness is not particularly limited, can
Various scopes are taken with the family in moderate thickness to very thin thickness.In this case base material
Thickness is preferably 1～1000 μm, more preferably 5～500 μm, particularly preferably 20～200 μm.
By using there is the base material of the transparency as base material, the transparency and excellent electric conductivity can be obtained
Conductive film.In the present invention, described " having the base material of the transparency " refers to, in wavelength 550nm
Under light transmittance be more than 50% base material.
It should be noted that in the present invention, light transmittance under wavelength 550nm for the base material can basis
The mensure of " light transmittance under wavelength 550nm for the conductive film " described in the embodiment of this specification
Method is measured.
It should be noted that as base material, it is possible to use possess the base material of priming coat.
In addition, for base material, the face that CNT dispersion to be coated can also be formed with conducting film is implemented
The surface hydrophilics such as glow discharge, Corona discharge Treatment or ozone process are processed.
In addition it is also possible to implement to give to the face of base material and the face opposition side of CNT dispersion to be coated
The hard painting of abrasion performance, high surface hardness, solvent resistance, stain resistance, fingerprint resistance etc. is processed.
<The formation of conducting film>
Conducting film can be by for example coating (coating work on above-mentioned base material by the CNT dispersion of the present invention
Sequence) and then so that the CNT dispersion on base material (drying process) is dried and is formed.
[painting process]
It is not particularly limited to the CNT dispersion of the present invention being coated the method on base material, Ke Yili
Use known coating process, the such as method described in Japanese Unexamined Patent Publication 2013-199419 publication.In addition,
For coating, can not only carry out once but carry out as needed repeatedly it is also possible to by different two
Plant coating process combination.Particularly preferred coating process can be enumerated：Bar coating, intaglio plate coating, spraying.
It should be noted that as described above, the CNT dispersion of the present invention and existing CNT dispersion
Compare and be capable of high concentration, the CNT of the per unit area of base material can be made with less application frequency
Coating weight is increased to desired value.
For coating thickness (wet thickness) when coating CNT dispersion on base material, as long as can ensure that
To the electric conductivity of film be then not particularly limited, preferably 0.001～50 μm, more preferably
0.005～10 μm, particularly preferably 0.01～3 μm.
In addition, the CNT of the per unit area as base material when coating CNT dispersion on base material
Coating weight, preferably 0.001mg/m2～50g/m2, more preferably 0.005mg/m2～10g/m2, especially
It is preferably 0.01mg/m2～3g/m2.
[drying process]
After CNT dispersion is coated on base material, by the method such as example air-drying, heating, reduce pressure,
So that the CNT dispersion on base material is dried, conducting film is formed on base material.As long as baking temperature can enter
Row solvent (C) based on vaporization removing, and for base material heat resisting temperature below, especially do not limit
Fixed.For example, in the case that base material uses above-mentioned plastic substrate material, baking temperature is preferably
0～250 DEG C, more preferably 15～150 DEG C, particularly preferably 80～150 DEG C.
<The removing of the dispersant in conducting film etc.>
Further, since the dispersion beyond macromolecule dispersing agent (B) can be comprised in the conducting film of the present invention
Agent or arbitrary adhesive material etc., accordingly it is also possible to especially removing these and improving conducting film
Electric conductivity.Method as removing dispersant etc., can be set forth in after forming conducting film on base material, will
To conductive film be immersed in washer solvent or to the conducting film spray washing solvent on base material
Method.As washer solvent, as long as dispersant to be removed etc. and will not can fully be dissolved
The solvent that CNT (A) is removed, is not particularly limited, and can enumerate for example：Water, alcohols, acetonitrile.
<The property of conducting film>
The conducting film of the present invention excellent in adhesion with base material.This conducting film is the CNT using the present invention
Dispersion liquid and formed, because the mechanical properties such as the film-strength of this conducting film, resistance to marring are excellent, its knot
Really, film is not easy destroyed in itself but rests on base material, therefore conclude that can show excellent strongly
Cementability.
In addition, the conducting film of the present invention obtains suitable dispersion due to the CNT (A) in conducting film, thus
Can be shown that excellent electric conductivity.In addition, the surface resistivity of the conducting film of the present invention is preferably 20 Ω/
Hereinafter, more preferably 10 Ω/below, as lower limit, usually 0.01 Ω/, more preferably
0.1Ω/□.It should be noted that the surface resistivity of the conducting film of the present invention can utilize this specification
Method described in embodiment is measured.
Conducting film for the present invention is it is also possible to measure to give by the CNT (A) contained by suitable adjustment
Bright property, for example, it is also possible to be used the above-mentioned base material with the transparency obtain as base material having transparent
The conductive film of property.Light transmittance under wavelength 550nm for such conductive film is preferably more than 50%,
More preferably more than 60%, more preferably more than 70%, even more preferably for more than 80%,
Particularly preferably more than 90%.It should be noted that the conductive film of the present invention is under wavelength 550nm
Light transmittance, it is possible to use the method described in the embodiment of this specification is measured.
<The purposes of conductive film>
As the purposes of the conductive film of the present invention, it is not particularly limited, for example, can be used for Japanese Unexamined Patent Publication
Purposes described in 2013-199419 publication.
And then, the conductive film of the present invention particularly suitable as dye-sensitized solar cell (DSC)
Photoelectricity electrode substrate, to electrode base board.
Embodiment
Hereinafter, enumerate embodiment the present invention is further illustrated, but the invention is not restricted to this
A little embodiments.
It is utilized respectively following method the surface resistivity of conducting film and the light transmittance of conductive film are carried out
Measure.And, it is utilized respectively following method to the stability of CNT dispersion, conducting film and base
The cementability of material is evaluated.
<Surface resistivity>
Using low-resistivity analyzer (Mitsubishi Chemical Analytech company system, trade name
" Loresta (registered trade mark)-GP MCP-T610 "), as described below using the method based on JIS K7194
Be determined.
Specifically, using four-terminal method, to conduction in 25 DEG C of temperature, the environment of humidity 20%RH
Property film the surface resistivity (film resistor) of conducting film being formed on base material be determined.
<Light transmittance>
Using spectrophotometer (Japanese light splitting company system V-570), the light transmittance under wavelength 550nm is carried out
Measure.
<The stability of CNT dispersion>
After preparing CNT dispersion, state after 25 DEG C stand 1 week for the visual observations, by following
Benchmark is evaluated.
A：Do not observe the change of dispersion liquid, be stable dispersity.
B：Confirm black foreign body, its cover container bottoms more than 0% and be less than 5% (area base
Accurate).
C：Confirm black foreign body, it covers the 5% of container bottoms less than 50% (area base
Accurate).
D：There is clear solution part in upper vessel portion, and confirmed more than the 50% of covering container bottoms
The black foreign body of (area benchmark).
<Conducting film and the cementability of base material>
Adhesive tape (Clear tape 12mm width) is pasted onto the conducting film side of conductive film, at 25 DEG C
After placing 2 hours, adhesive tape side is lifted with 90 ° of angle.Visual observations now conducting film with respect to
The exfoliated state of base material, and evaluated by following benchmark.
A：Do not observe stripping completely, cementability is good.
B：Observe stripping in conducting film more than 0% and less than 10% (area benchmark), but cementability is
Substantially the level having no problem in actually used.
C：In conducting film 10% observes stripping less than 40% (area benchmark), and cementability is
Level of problems in actually used.
D：Observe stripping in more than 40% (area benchmark) of conducting film, cementability is excessively poor water
Flat.
<Using material>
[CNT]
Employ following CNT.
CNT1：Single wall CNT (KH Chemicals HP purity 80%) BET specific surface area 620m2/g
CNT2：Single wall CNT (Meijo Nano Carbon SWNT SO) BET specific surface area 800m2/g
CNT3：SGCNT (is prepared according to following order).BET specific surface area 1050m2/g
[preparation of CNT3 (SGCNT)]
According to the International Publication No. record of No. 2006/011655, obtained by Super-growth method
CNT3(SGCNT).
For the CNT3 obtaining, BET specific surface area is 1050m2/ g (not opening), is utilizing Raman
In the mensure that spectrophotometer is carried out, in the distinctive 100～300cm of single wall CNT-1Lower wave number model
Enclose the spectrum that observed radial breathing modes (RBM).In addition, using transmission electron microscope randomly
Determine the diameter of 100 CNT3 as a result, average diameter (Av) is 3.3nm, diameter Distribution (3 σ)
It is 0.58 for 1.9nm, their ratio (3 σ/Av).
[dispersant]
In addition, as dispersant, except above-mentioned<Macromolecule dispersing agent (B)>The macromolecule dispersion of middle illustration
Beyond agent, employ following comparison dispersant A～F.
Relatively dispersant A：Sodium polyacrylate (weight average molecular weight 200,000)
Relatively dispersant B：Polystyrene ammonium (weight average molecular weight 20,000)
Relatively dispersing agent C：Carboxymethyl cellulose (weight average molecular weight 300,000, degree of etherification falling 0.6～0.8)
Relatively dispersant D：Dodecylbenzene sodium sulfonate (molecular weight 348.5)
Relatively dispersant E：Polyoxyethylene-to octyl phenyl ether (average degree of polymerization 10)
Relatively dispersant F：Sodium styrene sulfonate (90)/Malaysia acid disodium (10) copolymer (mol ratio=9/1,
Average degree of polymerization 20,000, number-average molecular weight 3,930,000 1700)
(embodiment 1)
<The preparation of carbon nano tube dispersion liquid>
The glass container of 10mL measures 6.25mg CNT1 (wherein CNT composition be 5.0mg),
10mg macromolecule dispersing agent D-5a (100 mass parts every with respect to CNT are 200 mass parts), adds and makees
For the distilled water 8ml and ethanol 2ml of solvent, and using 1N hydrochloric acid, pH is adjusted to 2.Through pH
After adjustment, utilize ultrasonic homogenizer under ice cooling, 4 in the bar of output 50W, 120 minutes
Carry out decentralized processing under part, be prepared for CNT dispersion.It should be noted that CNT in dispersion liquid
Concentration is 0.05 mass %, and the concentration of macromolecule dispersing agent is 0.1 mass %.Using said method evaluation
The stability of the CNT dispersion obtaining.Show the result in table 1.
<Conducting film and the manufacture of conductive film>
It is used rod coaters (#10) to be coated on the CNT dispersion obtaining and have passed through hydrophiling as base material
Surface treatment polyethylene terephthalate (PET) film (Japan spin (strain) company system A4100,
100 μm), A4 size) on.The CNT coating weight of the per unit area of base material is 10mg/m2.To apply
The base material of cloth CNT dispersion stands 10 minutes, further at 100 DEG C in room temperature, no-wind environment
It is dried 5 minutes in exsiccator, obtained the conductive film that conducting film is possessed on base material.Using above-mentioned side
Method is determined to surface resistivity, light transmittance, and using said method, conducting film is glued with base material
Connecing property is evaluated.Show the result in table 1.
(embodiment 2)
<The preparation of carbon nano tube dispersion liquid>
20mg CNT2,40mg macromolecule dispersing agent D-2 (phase is measured in the glass container of 10mL
For CNT, every 100 mass parts are 200 mass parts), add the distilled water 8ml as solvent and ethanol
2ml, and adjusted pH to 1.6 using 1N nitric acid.After pH adjusts, profit under ice cooling, 4
Carry out decentralized processing with ultrasonic homogenizer in output 50W, under conditions of 120 minutes, be prepared for
CNT dispersion.It should be noted that the CNT concentration in dispersion liquid is 0.2 mass %, macromolecule
The concentration of dispersant is 0.4 mass %.Have rated stablizing of the CNT dispersion obtaining using said method
Property.Show the result in table 1.
<The manufacture of conductive film>
It is used rod coaters (#10) to be coated on the CNT dispersion obtaining and have passed through hydrophiling as base material
Surface treatment polyethylene terephthalate (PET) film (Japan spin (strain) company system A4100,
100 μm), A4 size) on.The CNT coating weight of the per unit area of base material is 32mg/m2.To apply
The base material of cloth CNT dispersion stands 10 minutes, further at 100 DEG C in room temperature, no-wind environment
It is dried 5 minutes in exsiccator, obtained the conductive film that conducting film is possessed on base material.Using above-mentioned side
Method is determined to surface resistivity, light transmittance, and using said method, conducting film is glued with base material
Connecing property is evaluated.Show the result in table 1.
(embodiment 3～8)
Replace macromolecule dispersing agent D-2 and employ respectively macromolecule dispersing agent D-4, D-5a, D-6,
D-8, D-12, D-15, in addition, are prepared for CNT dispersion similarly to Example 2, and make
Conducting film and conductive film are made.It should be noted that the CNT concentration in dispersion liquid is 0.2 matter
Amount %, the concentration of macromolecule dispersing agent is 0.4 mass %.And then, similarly to Example 1 to each
Project is determined, evaluates.Show the result in table 1.
(embodiment 9)
<The preparation of carbon nano tube dispersion liquid>
10mg CNT3,20mg macromolecule dispersing agent D-5a (phase is measured in the glass container of 10mL
For CNT, every 100 mass parts are 200 mass parts), add the distilled water 8ml as solvent and ethanol
2ml, and adjusted pH to 1.6 using 1N nitric acid.After pH adjusts, profit under ice cooling, 4
Carry out decentralized processing with ultrasonic homogenizer in output 50W, under conditions of 120 minutes, be prepared for
CNT dispersion.It should be noted that the CNT concentration in dispersion liquid is 0.1 mass %, macromolecule
The concentration of dispersant is 0.2 mass %.Have rated stablizing of the CNT dispersion obtaining using said method
Property.Show the result in table 1.
<Conducting film and the manufacture of conductive film>
It is used rod coaters (#10) to be coated on the CNT dispersion obtaining and have passed through hydrophiling as base material
Surface treatment polyethylene terephthalate (PET) film (Japan spin (strain) company system A4100,
100 μm), A4 size) on.The CNT coating weight of the per unit area of base material is 32mg/m2.To apply
The base material of cloth CNT dispersion stands 10 minutes, further at 100 DEG C in room temperature, no-wind environment
It is dried 5 minutes in exsiccator, obtained the conductive film that conducting film is possessed on base material.To sheet resistance
Rate, light transmittance carry out said determination, and using said method, the cementability of conducting film and base material are carried out
Evaluate.Show the result in table 1.
(embodiment 10)
The amount making CNT3 is 20mg, and using 40mg macromolecule dispersing agent D-5b (with respect to CNT
Every 100 mass parts are 200 mass parts) replace macromolecule dispersing agent D-5a, in addition, with embodiment
9 are equally prepared for CNT dispersion, and have manufactured conducting film and conductive film.It should be noted that
CNT concentration in dispersion liquid is 0.2 mass %, and the concentration of macromolecule dispersing agent is 0.4 mass %.Enter
And, similarly to Example 1 projects are determined, evaluate.Show the result in table 1.
(embodiment 11,12)
Macromolecule dispersing agent D-5b is replaced to employ macromolecule dispersing agent D-6, D-11 respectively, except this
In addition, it is prepared for CNT dispersion similarly to Example 10, and manufactured conducting film and conductive film.
And then, similarly to Example 1 projects are determined, evaluate.Show the result in table 1.
(embodiment 13)
The amount of CNT3 is made to be 15mg and the use level of macromolecule dispersing agent D-5a is changed into 30mg (phase
For CNT, every 100 mass parts are 200 mass parts), in addition, it is prepared for similarly to Example 9
CNT dispersion.Then, coating CNT dispersion makes the CNT coating weight of the per unit area of base material
For 394mg/m2, in addition, manufactured conducting film and conductive film similarly to Example 9.Need
It is noted that the CNT concentration in dispersion liquid is 0.15 mass %, the concentration of macromolecule dispersing agent is
0.3 mass %.And then, similarly to Example 1 projects are determined, evaluate.By result
It is shown in table 1.
(comparative example 1)
<The making of carbon nano tube dispersion liquid>
The glass container of 10mL measures 25mg CNT1 (wherein CNT composition be 20mg),
40mg compares dispersant A (100 mass parts every with respect to CNT are 200 mass parts), adds as molten
The distilled water 8ml of agent simultaneously adds ethanol 2ml, and adjust pH to 2 using 1N hydrochloric acid.Through pH
After adjustment, utilize ultrasonic homogenizer under ice cooling, 4 in the bar of output 50W, 120 minutes
Carry out decentralized processing under part, be prepared for CNT dispersion.
It should be noted that the CNT concentration in dispersion liquid is 0.20 mass %, macromolecule dispersing agent
Concentration is 0.4 mass %.However, as described in table 1, the stability of dispersion liquid is excessively poor,
Fail to produce the conducting film with homogeneous thickness and conductive film.
(comparative example 2)
Replace comparing dispersant A and employing and compare dispersant B, in addition, same with comparative example 1
Be prepared for CNT dispersion.However, as described in table 1, the stability of dispersion liquid is very
Difference, fails to produce the conducting film with homogeneous thickness and conductive film.
(comparative example 3)
The use level comparing dispersant B is made to be that (100 mass parts every with respect to CNT are 400 matter to 80mg
Amount part), in addition, it has been prepared as CNT dispersion with comparative example 1.CNT in dispersion liquid
Concentration is 0.20 mass %, and the concentration of macromolecule dispersing agent is 0.8 mass %.In addition, with embodiment 1
Conducting film and conductive film are similarly manufactured.The CNT coating weight of the per unit area of base material is
40mg/m2.And then, similarly to Example 1 projects are determined, evaluate.Result is shown
In table 1.
(comparative example 4)
Replace comparing dispersant A and employing and compare dispersing agent C, in addition, same with comparative example 1
Be prepared for CNT dispersion.However, as described in table 1, the stability of dispersion liquid is very
Difference, fails to produce the conducting film with homogeneous thickness and conductive film.
(comparative example 5)
Replace comparing dispersant B and employing and compare dispersing agent C, in addition, same with comparative example 3
Be prepared for CNT dispersion.CNT concentration in dispersion liquid is 0.20 mass %, macromolecule dispersing agent
Concentration be 0.8 mass %.In addition, having manufactured conducting film and conductive film similarly to Example 1.
The CNT coating weight of the per unit area of base material is 40mg/m2.And then, right similarly to Example 1
Projects are determined, evaluate.Show the result in table 1.
(comparative example 6,7)
Replace comparing dispersant B and employing respectively and compare dispersant D, E, in addition, and compare
Example 3 has been prepared as CNT dispersion.CNT concentration in dispersion liquid is 0.20 mass %, high score
The concentration of sub- dispersant is 0.8 mass %.However, as described in table 1, the stablizing of dispersion liquid
Property is excessively poor, fails to produce the conducting film with homogeneous thickness and conductive film.
(comparative example 8)
Replace comparing dispersant A and employing and compare dispersant F, in addition, same with comparative example 1
Be prepared for CNT dispersion.The concentration of the CNT in dispersion liquid is 0.20 mass %, and macromolecule disperses
The concentration of agent is 0.4 mass %.In addition, having manufactured conducting film and conductive film similarly to Example 1.
The CNT coating weight of the per unit area of base material is 40mg/m2.However, as described in table 1,
Some are poor for the stability of dispersion liquid, in addition, cementability is poor.
According to table 1, for employ containing monomeric unit containing sulfonic group and with specific contain than
Example the macromolecule dispersing agent containing olefinic unsaturated aliphatic carboxylic monomer unit (B) embodiment 1～13 and
Speech, the stability of CNT dispersion and conducting film are excellent in adhesion with base material.
On the other hand, employ in comparative example 1,2,4,6,7 do not have monomeric unit containing sulfonic group and
The dispersant of any one of olefinic unsaturated aliphatic carboxylic monomer unit or neither have containing sulfonic group
Monomeric unit do not have yet olefinic unsaturated aliphatic carboxylic monomer unit dispersant it is known that, they with
It is excessively poor that embodiment 1～13 compares dispersibility.
Additionally, ensure that the steady of CNT dispersion by improving the concentration of dispersant in comparative example 3,5
Qualitative, but comparative example 3 employs and neither has monomeric unit containing sulfonic group nor have olefinic unsaturated lipid
The dispersant of aliphatic carboxylic acid's monomeric unit, comparative example 5 employ with olefinic unsaturated aliphatic carboxylic acid list
Body unit but there is no the dispersant containing sulfonic group monomeric unit, the conducting film in gained conductive film and base
The cementability extreme difference of material.
Additionally, employing in comparative example 8 containing monomeric unit containing sulfonic group and olefinic unsaturated aliphatic carboxylic
Both acid monomer units but the content ratio of olefinic unsaturated aliphatic carboxylic monomer unit are 20 moles of %
Following macromolecule dispersing agent is although ensure that the stability of CNT dispersion, but the electric conductivity obtaining
Conducting film in film and the cementability extreme difference of base material.
Industrial applicibility
According to the present invention it is possible to providing excellent in stability and being formed excellent in adhesion with base material
Conducting film carbon nano tube dispersion liquid.
In addition, according to the present invention it is possible to providing and conducting film base material excellent in adhesion and possessing
The conductive film of this conducting film.
Claims (11)
1. a kind of carbon nano tube dispersion liquid, it comprises：
CNT (A),
Fractionated polymer containing monomeric unit containing sulfonic group and olefinic unsaturated aliphatic carboxylic monomer unit
Powder (B) and
Solvent (C),
Olefinic unsaturated aliphatic carboxylic monomer unit described in described macromolecule dispersing agent (B) containing than
Example higher than 20 moles of % and is 90 moles of below %.
2. carbon nano tube dispersion liquid according to claim 1, wherein, described macromolecule dispersing agent (B)
In described monomeric unit containing sulfonic group be monomeric unit from aromatic sulphonic acid or its salt.
3. carbon nano tube dispersion liquid according to claim 1 and 2, wherein, described fractionated polymer
Described olefinic unsaturated aliphatic carboxylic monomer unit in powder (B) is at least one in being selected from the group：
Acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and their salt.
4. the carbon nano tube dispersion liquid according to any one of claims 1 to 3, wherein, described height
Contain described in dispersal agent molecule (B) sulfonic group monomeric unit content ratio be 10 moles of % less than
80 moles of %.
5. the carbon nano tube dispersion liquid according to any one of Claims 1 to 4, wherein, described height
In dispersal agent molecule (B), the described content ratio containing sulfonic group monomeric unit and described olefinic unsaturated lipid
The ratio of the content ratio of aliphatic carboxylic acid's monomeric unit is 0.5 less than 4.
6. the carbon nano tube dispersion liquid according to any one of Claims 1 to 5, wherein, described carbon
Nanotube (A) comprises at least one of SWCN and double-walled carbon nano-tube.
7. the carbon nano tube dispersion liquid according to any one of claim 1～6, wherein, described molten
Agent (C) comprises water, and, the pH of described carbon nano tube dispersion liquid is more than 0.1 and less than 8.
8. the carbon nano tube dispersion liquid according to any one of claim 1～7, wherein, with respect to
Every 100 mass parts of CNT (A), the content of described macromolecule dispersing agent (B) be more than 50 mass parts and
Below 1000 mass parts.
9. a kind of conducting film, it is that usage right requires the CNT dispersion any one of 1～8
Obtained from liquid.
10. conducting film according to claim 9, its surface resistivity is 20 Ω/below.
A kind of 11. conductive films, it possesses：
Base material and
Conducting film on described base material,
Described conducting film is the conducting film described in claim 9 or 10.
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| PCT/JP2015/000401 WO2015115102A1 (en) | 2014-01-31 | 2015-01-29 | Carbon nanotube dispersion liquid, conductor film and conductive film |
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| US (2) | US10870766B2 (en) |
| EP (1) | EP3100977B1 (en) |
| JP (1) | JP6493223B2 (en) |
| KR (1) | KR20160114594A (en) |
| CN (2) | CN110589808B (en) |
| TW (1) | TWI653194B (en) |
| WO (1) | WO2015115102A1 (en) |
Cited By (5)
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|---|---|---|---|---|
| CN107417852A (en) * | 2017-07-20 | 2017-12-01 | 河南师范大学 | A kind of Carbon nano-tube dispersant and preparation method thereof and the application in cell conductive paste is prepared |
| CN113330066A (en) * | 2019-02-01 | 2021-08-31 | 日本瑞翁株式会社 | Dispersion liquid, conductive film, method for producing same, electrode, and solar cell |
| CN113727845A (en) * | 2019-04-25 | 2021-11-30 | 丸爱株式会社 | Sheet for electronic component conveying tray/carrier tape and electronic component conveying tray/carrier tape using the same |
| CN114728795A (en) * | 2019-11-15 | 2022-07-08 | 花王株式会社 | Method for producing semiconductor-type single-walled carbon nanotube dispersion |
| CN114728794A (en) * | 2019-11-15 | 2022-07-08 | 花王株式会社 | Method for producing semiconductor-type single-walled carbon nanotube dispersion |
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| JP6794903B2 (en) * | 2017-03-31 | 2020-12-02 | 日本ゼオン株式会社 | Bonding method |
| JP7018661B2 (en) * | 2017-06-09 | 2022-02-14 | 国立研究開発法人産業技術総合研究所 | Method for manufacturing carbon nanotube dispersion liquid, carbon nanotube dispersion liquid, and method for manufacturing carbon nanotube composite film |
| US20200102697A1 (en) * | 2017-09-28 | 2020-04-02 | Zeon Corporation | Sheet and method of manufacturing the same |
| JP7059001B2 (en) * | 2017-12-28 | 2022-04-25 | 花王株式会社 | Dispersant for single-walled carbon nanotubes and single-walled carbon nanotube dispersion liquid using it |
| JP7131970B2 (en) * | 2018-06-05 | 2022-09-06 | 花王株式会社 | Carbon nanotube aqueous dispersion |
| US20230245797A1 (en) | 2019-10-15 | 2023-08-03 | Kyoto University | Conductive film, dispersion, manufacturing methods for these, and device including conductive film |
| WO2022009805A1 (en) * | 2020-07-09 | 2022-01-13 | 大日精化工業株式会社 | Carbon material dispersion |
| KR20220146167A (en) * | 2021-04-23 | 2022-11-01 | 삼성전자주식회사 | Carbon nanotube single layer, preparing method thereof, and electronic device including the same |
| KR102463829B1 (en) * | 2022-06-21 | 2022-11-04 | 한국산노프코 주식회사 | Dispersing agent for high-concentration aqueous carbon nanotubes and carbon nanotube dispersion containing the same |
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| CN113330066A (en) * | 2019-02-01 | 2021-08-31 | 日本瑞翁株式会社 | Dispersion liquid, conductive film, method for producing same, electrode, and solar cell |
| CN113330066B (en) * | 2019-02-01 | 2024-01-30 | 日本瑞翁株式会社 | Dispersion, conductive film, method for producing same, electrode, and solar cell |
| CN113727845A (en) * | 2019-04-25 | 2021-11-30 | 丸爱株式会社 | Sheet for electronic component conveying tray/carrier tape and electronic component conveying tray/carrier tape using the same |
| CN114728795A (en) * | 2019-11-15 | 2022-07-08 | 花王株式会社 | Method for producing semiconductor-type single-walled carbon nanotube dispersion |
| CN114728794A (en) * | 2019-11-15 | 2022-07-08 | 花王株式会社 | Method for producing semiconductor-type single-walled carbon nanotube dispersion |
Also Published As
| Publication number | Publication date |
|---|---|
| US20160340521A1 (en) | 2016-11-24 |
| US11186733B2 (en) | 2021-11-30 |
| JP6493223B2 (en) | 2019-04-03 |
| EP3100977B1 (en) | 2023-05-03 |
| WO2015115102A1 (en) | 2015-08-06 |
| CN110589808B (en) | 2023-06-30 |
| US20210062014A1 (en) | 2021-03-04 |
| US10870766B2 (en) | 2020-12-22 |
| TW201532960A (en) | 2015-09-01 |
| KR20160114594A (en) | 2016-10-05 |
| JPWO2015115102A1 (en) | 2017-03-23 |
| EP3100977A4 (en) | 2017-10-18 |
| TWI653194B (en) | 2019-03-11 |
| EP3100977A1 (en) | 2016-12-07 |
| CN110589808A (en) | 2019-12-20 |
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